A hyperspectral imaging method was developed that allowed the identification of heterogeneous plasmon response from 50 nm diameter gold colloidal particles on a conducting substrate in a transparent three-electrode spectroelectrochemical cell under non-Faradaic conditions. At cathodic potentials, we identified three distinct behaviors from different nanoparticles within the same sample: irreversible chemical reactions, reversible chemical reactions, and reversible charge density tuning. The irreversible reactions in particular would be difficult to discern in alternate methodologies. Additional heterogeneity was observed when single nanoparticles demonstrating reversible charge density tuning in the cathodic regime were measured dynamically in anodic potential ranges. Some nanoparticles that showed charge density tuning in the cathodic range also showed signs of an additional chemical tuning mechanism in the anodic range. The expected changes in nanoparticle free-electron density were modeled using a charge density-modified Drude dielectric function and Mie theory, a commonly used model in colloidal spectroelectrochemistry. Inconsistencies between experimental results and predictions of this common physical model were identified and highlighted. The broad range of responses on even a simple sample highlights the rich experimental and theoretical playgrounds that hyperspectral single-particle electrochemistry opens.

Redox electrochemistry was used to reversibly tune the optical properties of plasmonic core-shell nanoparticles and dimers.

Strong light-absorbing properties allow plasmonic metal nanoparticles to serve as antennas for other catalysts to function as photocatalysts. To achieve plasmonic photocatalysis, the hot charge carriers created when light is absorbed must be harnessed before they decay through internal relaxation pathways. We demonstrate the role of photogenerated hot holes in the oxidative dissolution of individual gold nanorods with millisecond time resolution while tuning charge-carrier density and photon energy using snapshot hyperspectral imaging. We show that light-induced hot charge carriers enhance the rate of gold oxidation and subsequent electrodissolution. Importantly, we distinguish how hot holes generated from interband transitions versus hot holes around the Fermi level contribute to photooxidative dissolution. The results provide new insights into hot-hole-driven processes with relevance to photocatalysis while emphasizing the need for statistical descriptions of nonequilibrium processes on innately heterogeneous nanoparticle supports.

Plasmonic nanoparticles offer promise in photoelectrochemistry by enhancing the rate and selectivity of reactions and in sensing by responding optically to local reactions. Optical electrochemical measurements at the single-particle level are necessary for understanding and eventually controlling the role of plasmons in such complex environments. Recently, researchers have developed techniques to optically measure electrochemical reactions at the surface of single nanoparticles and individual aggregates, allowing for the high-throughput screening necessary to resolve subpopulations of active nanoparticle catalysts and identify active sites on aggregate structures. This review highlights single-nanoparticle and nanoparticle aggregate electrochemical techniques and how they can be used to isolate and elucidate the role of surface plasmons in enhancing catalyst activity and sensing electrochemical processes at the nanoscale.